CN1841195A - Radiation-sensitive resin composition, protrusions and partitions formed from the same, method for forming the same, and liquid crystal display element - Google Patents

Abstract

The object of this invention is to provide a radiation-sensitive resin composition which is suitably used for simultaneously forming protrusions and spacers of a vertical alignment liquid crystal display element. The radiation-sensitive resin composition for simultaneously forming the protrusions and the spacers for the vertical alignment liquid crystal display element contains: a copolymer [A] of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride (a1), an unsaturated compound having an epoxy group or an oxetanyl group (a2) and an olefinically unsaturated compound other than (a1) and (a2) (a3); and a photo-cationic polymerization initiator [B].

Description

Radiation-sensitive resin composition, protrusions and partitions formed from the same, method for forming the same, and liquid crystal display element

technical field

The present invention relates to a radiation-sensitive resin composition for forming protrusions and/or spacers used in vertical alignment liquid crystal display elements, protrusions and spacers used in vertical alignment liquid crystal display elements formed from the composition A spacer, a vertical alignment type liquid crystal display element comprising the protrusion and/or the spacer, and a method of forming the protrusion and/or the spacer.

Background technique

Liquid crystal display elements are widely used in flat panel displays. In recent years, with the spread of OA equipment such as personal computers and word processors, and liquid crystal televisions, the display quality requirements for TFT (thin film transistor) liquid crystal displays (TFT-LCDs) have become increasingly stringent. Among TFT-LCDs, TN (Twisted Nematic) type LCDs are the most popular now. This LCD is manufactured by the following method: on the two outer sides of two substrates with transparent electrodes (hereinafter referred to as "transparent electrode substrates"), polarizing films with orientation directions different by 90 degrees are arranged respectively, and An alignment film is arranged inside the electrode substrate; a nematic liquid crystal is arranged between the two alignment films, and the alignment direction of the liquid crystal is twisted from one electrode side to the other electrode side at an angle of 90 degrees. When unpolarized light is incident in this state, linearly polarized light that has passed through one polarizer passes through the liquid crystal, and its polarization direction is changed so that it can pass through the other polarizer to form a bright state. Then, when a voltage is applied to both electrodes to make the liquid crystal molecules stand upright, the linearly polarized light reaching the liquid crystal passes directly without passing through the other polarizing plate, resulting in a dark state. Thereafter, when the application of voltage is stopped, it returns to the bright state.

Although, due to technological progress in recent years, such TN-type LCDs have become comparable to or superior to cathode ray tubes (CRTs) in aspects such as frontal contrast and color reproducibility. However, there is still a big problem to be solved for TN type LCD, that is narrow viewing angle. As a method for solving such a problem, an MVA (Multi-domain Vertically Aligned) type LCD (Vertical Alignment Liquid Crystal Display) has been developed. As described in Non-Patent Document 1 and Patent Document 1, the MVA-type LCD is not the optical rotation mode of the TN-type LCD, but a dual-mode LCD that combines negative-type liquid crystals with negative dielectric constant anisotropy and alignment films in the vertical direction. Refractive mode LCD, using this kind of birefringent mode LCD; even in the state where no voltage is applied, the liquid crystal alignment direction at the position close to the alignment film can be kept approximately in the vertical direction, so the contrast ratio, viewing angle, etc. are excellent, and It is not necessary to perform polishing treatment for aligning liquid crystals, etc., and it is also excellent in terms of production steps.

In the MVA type LCD, in order to allow liquid crystals to take multiple alignment directions in one pixel area, as a method of area limitation, the electrodes on the display side can be electrodes with slits in one pixel area, and the electrodes on the light incident side In the same pixel area on the electrode substrate, protrusions with slopes (for example, triangular pyramid shapes, semi-convex lens shapes, etc.) are formed at positions different from the electrode slits. In addition, in current liquid crystal displays, spherical or rod-shaped separators such as resin and ceramics are generally used to maintain a constant gap (cell gap) between two transparent electrode substrates. When laminating two transparent electrode substrates, separators can be spread on any one of the substrates, and the cell gap is determined according to the diameter of the separators.

In addition, in order to avoid problems such as uneven cell gaps caused by differences in spacer diameters, Patent Document 2 also discloses a method of using photoresist materials to form protrusions and spacers. This method has the following advantages: it can be microfabricated and is easy to control shape. However, Patent Document 2 does not specifically describe the composition of the photoresist material, nor does it indicate the properties of the formed protrusions and spacers.

[Non-Patent Document 1] Yuhiro Takeda, Liquid Crystal, Liquid Crystal Society of Japan, April 25, 1999, Vol.3, No.2, 117

[Patent Document 1] Japanese Unexamined Patent Publication No. 11-258605

[Patent Document 2] JP-A-2001-201750

The properties required for the photoresist used in the formation of protrusions and spacers used in vertical alignment liquid crystal display elements include the following. That is, in addition to the appropriate cross-sectional shape of the protrusions and spacers, tolerance to the solvent used in the subsequent alignment film formation process, resistance to heat applied in the alignment film formation process, transparency, resolution, and residue are required. The film rate and other properties are high. In addition, the resulting vertical alignment type liquid crystal display element is also required to be excellent in orientation, voltage retention, and the like. The present applicant has proposed a radiation-sensitive resin composition for simultaneously forming protrusions and spacers, the resin composition comprising [A] consisting of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride, (a2) containing Copolymers formed of epoxy-based unsaturated compounds and (a3) unsaturated compounds other than these, [B] unsaturated polymerizable compounds and [C] radiation-sensitive polymerization initiators; also proposed are resin compositions made of the The formed protrusions and partitions, and a liquid crystal display element including the protrusions and partitions (see Patent Document 3). However, only a radiation-sensitive resin composition useful for the formation of protrusions and partitions of a vertical alignment type liquid crystal display element has been developed, and the development of a radiation-sensitive resin composition compatible with the rapid popularization of TFT-LCD and increasingly stringent performance requirements can be achieved. A novel radiation-sensitive resin composition forming protrusions and spacers having excellent properties is becoming an important technical subject.

[Patent Document 3] JP-A-2003-29405

Contents of the invention

The present invention was made in view of the above problems, and the object is to provide a radiation-sensitive resin composition for forming protrusions and/or spacers used in a vertical alignment type liquid crystal display element, more specifically, to provide a , Excellent resolution and remaining film rate, can form protrusions and partitions with excellent pattern shape, heat resistance, solvent resistance, transparency, etc., and can obtain vertical alignment liquid crystal display elements with excellent orientation, voltage retention, etc. A radiation-sensitive resin composition, and a method for forming protrusions and/or spacers used in a vertical alignment type liquid crystal display element using the radiation-sensitive resin composition.

According to the present invention, the above-mentioned objects and advantages of the present invention, the first one is realized by a radiation-sensitive resin composition for forming protrusions and/or spacers used in vertical alignment type liquid crystal display elements, the radiation-sensitive The resin composition is characterized in that: comprising,

[A] A copolymer obtained by copolymerizing the following (a1) to (a3) (hereinafter referred to as "copolymer [A]), wherein (a1) is an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (hereinafter , referred to as "compound (a1)"),

(a2) is an unsaturated compound (hereinafter referred to as "compound (a2)") having an epoxy group or an oxetanyl group,

(a3) is an olefinic unsaturated compound other than the above-mentioned components (a1) and (a2) (hereinafter referred to as "compound (a3)"); and

[B] Photocationic polymerization initiator.

The second object and advantages of the present invention are achieved by a protrusion used in a vertical alignment type liquid crystal display device formed of the above-mentioned radiation-sensitive resin composition.

The third object and advantage of the present invention are achieved by a separator used in a vertical alignment type liquid crystal display device formed of the above-mentioned radiation-sensitive resin composition.

The fourth object and advantages of the present invention are achieved by a vertical alignment type liquid crystal display device comprising the above-mentioned protrusions and/or the above-mentioned spacers.

The object and advantage of the present invention, the 5th is realized by the method for forming protrusion and/or spacer, and this method is characterized in that comprising at least the following steps:

(1) A step of forming a coating film of the radiation-sensitive composition described in Item 1 on a substrate;

(2) A step of irradiating at least a part of the coating film with radiation;

(3) Developing process;

(4) Heating process.

The radiation-sensitive resin composition used to form the protrusions and/or partitions used in the vertical alignment type liquid crystal display element of the present invention can be formed with excellent resolution and residual film rate, and the pattern shape, heat resistance, solvent resistance, It can provide protrusions and/or partitions excellent in transparency, etc., and can also provide a vertical alignment type liquid crystal display element excellent in orientation, voltage retention, etc. In addition, the method for forming the protrusions and/or partitions used in the vertical alignment type liquid crystal display element of the present invention can be finely processed, and the shape and size (height and bottom size) can be easily controlled, and the pattern shape can be stably and productively formed, Fine protrusions and partitions excellent in heat resistance, solvent resistance, transparency, etc., and also can provide a vertical alignment type liquid crystal display element excellent in orientation, voltage retention, etc.

Description of drawings

A-C in FIG. 1 are schematic diagrams showing the cross-sectional shapes of protrusions and partitions, respectively.

Fig. 2 is a schematic view showing a cross-sectional shape of a vertical alignment type liquid crystal display element having protrusions and spacers.

Detailed ways

Hereinafter, each component of the radiation-sensitive resin composition of this invention is demonstrated in detail.

Copolymer (A)

The copolymer [A] is synthesized by radically polymerizing the compound (a1), the compound (a2) and the compound (a3) in a solvent in the presence of a polymerization initiator.

The copolymer [A] used in the present invention preferably contains 5 to 40% by weight of the structural unit derived from the compound (a1), particularly preferably 10 to 35% by weight. A copolymer having less than 5% by weight of the constituent units is difficult to dissolve in an alkaline aqueous solution, and a copolymer having more than 40% by weight tends to have too high solubility in an alkaline aqueous solution.

Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and Their acid anhydrides, succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, etc. Mono[(meth)acryloyloxyalkyl]esters of acids, mono(meth)acrylates of polymers having carboxyl and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate class etc. Among them, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used from the viewpoints of copolymerization reactivity, solubility in an alkaline aqueous solution, and easy availability. They can be used alone or in combination.

The copolymer [A] used in the present invention preferably contains 5 to 60% by weight of the structural unit derived from the compound (a2), particularly preferably 10 to 50% by weight. When the constituent unit is less than 5% by weight, the heat resistance of the obtained coating film tends to decrease, while on the other hand, when it exceeds 60% by weight, the storage stability of the copolymer tends to decrease.

Examples of the compound (a2) include an epoxy group-containing unsaturated compound or an oxetanyl group-containing unsaturated compound.

Examples of unsaturated compounds containing epoxy groups include glycidyl acrylate, 2-methylglycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl acrylate, Epoxy (cyclo)alkyl acrylates such as 6,7-epoxyheptyl acrylate and 3,4-epoxycyclohexyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate , 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate and other epoxy (cyclo)alkyl methacrylates Esters, α-glycidyl ethacrylate, α-glycidyl propyl acrylate, α-glycidyl butyl acrylate, 6,7-epoxyheptyl α-ethacrylate, α-ethyl 3,4-epoxycyclohexyl acrylate and other α-alkyl acrylate epoxy (cyclo)alkyl esters; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- - Glycidyl ethers such as vinylbenzyl glycidyl ether and the like.

Examples of unsaturated compounds containing an oxetanyl group include 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethane oxetane, 3-(methacryloxymethyl)-3-methyloxetane, 3-(methacryloxymethyl)-2-methyloxetane Butane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane Butane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane alkane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxymethyl)-2,2,4,4 -Tetrafluorooxetane, 3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-3-ethyloxetane , 2-ethyl-3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-2-trifluoromethyloxetane, 3 -(methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxyethyl)-2-phenyl-oxetane, 2, 2-Difluoro-3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-2,2,4-trifluorooxetane Alkane, 3-(methacryloyloxyethyl)-2,2,4,4-tetrafluorooxetane,

2-(methacryloyloxymethyl)oxetane, 2-methyl-2-(methacryloyloxymethyl)oxetane, 3-methyl-2-(methyl methacryloyloxymethyl)oxetane, 4-methyl-2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)- 2-trifluoromethyloxetane, 2-(methacryloyloxymethyl)-3-trifluoromethyloxetane, 2-(methacryloyloxymethyl)- 4-trifluoromethyloxetane, 2-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 2-(methacryloyloxymethyl)- 3-Pentafluoroethyloxetane, 2-(methacryloyloxymethyl)-4-pentafluoroethyloxetane, 2-(methacryloyloxymethyl)- 2-Phenyloxetane, 2-(methacryloyloxymethyl)-3-phenyloxetane, 2-(methacryloyloxymethyl)-4-phenyl Oxetane, 2,3-difluoro-2-(methacryloyloxymethyl)oxetane, 2,4-difluoro-2-(methacryloyloxymethyl) base) oxetane, 3,3-difluoro-2-(methacryloyloxymethyl)oxetane, 3,4-difluoro-2-(methacryloyloxy (methyl)oxetane, 4,4-difluoro-2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-3 , 3,4-trifluorooxetane, 2-(methacryloyloxymethyl)-3,4,4-trifluorooxetane, 2-(methacryloyloxy methyl)-3,3,4,4-tetrafluorooxetane,

2-(Methacryloyloxyethyl)oxetane, 2-(2-(2-methyloxetanyl))ethyl methacrylate, 2-(2- (3-Methyloxetanyl))ethyl ester, 2-(methacryloyloxyethyl)-2-methyloxetane, 2-(methacryloyloxyethyl )-4-methyloxetane, 2-(methacryloyloxyethyl)-2-trifluoromethyloxetane, 2-(methacryloyloxyethyl)- 3-trifluoromethyloxetane, 2-(methacryloyloxyethyl)-4-trifluoromethyloxetane, 2-(methacryloyloxyethyl)- 2-Pentafluoroethyloxetane, 2-(methacryloyloxyethyl)-3-pentafluoroethyloxetane, 2-(methacryloyloxyethyl)- 4-pentafluoroethyloxetane, 2-(methacryloyloxyethyl)-2-phenyloxetane, 2-(methacryloyloxyethyl)-3- Phenyloxetane, 2-(methacryloyloxyethyl)-4-phenyloxetane, 2,3-difluoro-2-(methacryloyloxyethyl ) oxetane, 2,4-difluoro-2-(methacryloyloxyethyl)oxetane, 3,3-difluoro-2-(methacryloyloxy Ethyl)oxetane, 3,4-difluoro-2-(methacryloyloxyethyl)oxetane, 4,4-difluoro-2-(methacryloyl Oxyethyl)oxetane, 2-(methacryloyloxyethyl)-3,3,4-trifluorooxetane, 2-(methacryloyloxyethyl )-3,4,4-trifluorooxetane, 2-(methacryloyloxyethyl)-3,3,4,4-tetrafluorooxetane and other methacrylic acid Esters;

3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-3- Methyloxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane alkane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 3-(propylene Acyloxymethyl)-2,2-difluorooxetane, 3-(acryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(propylene Acyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl) -3-Ethyl-oxetane, 2-ethyl-3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl)-2-trifluoromethyl Oxetane, 3-(acryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxyethyl)-2-phenyloxetane, 2,2-Difluoro-3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl)-2,2,4-trifluorooxetane, 3-(acryloyloxyethyl)-2,2,4,4-tetrafluorooxetane,

2-(acryloyloxymethyl)oxetane, 2-methyl-2-(acryloyloxymethyl)oxetane, 3-methyl-2-(acryloyloxymethyl base) oxetane, 4-methyl-2-(acryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)-2-trifluoromethyloxetane Alkanes, 2-(acryloyloxymethyl)-3-trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane, 2- (Acryloyloxymethyl)-2-pentafluoroethyloxetane, 2-(acryloyloxymethyl)-3-pentafluoroethyloxetane, 2-(acryloyloxy methyl)-4-pentafluoroethyloxetane, 2-(acryloyloxymethyl)-2-phenyloxetane, 2-(acryloyloxymethyl)-3 -Phenyloxetane, 2-(acryloyloxymethyl)-4-phenyloxetane, 2,3-difluoro-2-(acryloyloxymethyl)oxetane Cyclobutane, 2,4-difluoro-2-(acryloyloxymethyl)oxetane, 3,3-difluoro-2-(acryloyloxymethyl)oxetane alkane, 3,4-difluoro-2-(acryloyloxymethyl)oxetane, 4,4-difluoro-2-(acryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)-3,3,4-trifluorooxetane, 2-(acryloyloxymethyl)-3,4,4-trifluorooxetane Alkane, 2-(acryloyloxymethyl)-3,3,4,4-tetrafluorooxetane,

2-(acryloxyethyl)oxetane, 2-(2-(2-methyloxetanyl))ethyl methacrylate, 2-(2-(3 -Methyloxetanyl))ethyl ester, 2-(acryloyloxyethyl)-2-methyloxetane, 2-(acryloyloxyethyl)-4-methyl Oxetane, 2-(acryloyloxyethyl)-2-trifluoromethyloxetane, 2-(acryloyloxyethyl)-3-trifluoromethyloxetane Alkanes, 2-(acryloyloxyethyl)-4-trifluoromethyloxetane, 2-(acryloyloxyethyl)-2-pentafluoroethyloxetane, 2- (Acryloyloxyethyl)-3-pentafluoroethyloxetane, 2-(acryloyloxyethyl)-4-pentafluoroethyloxetane, 2-(acryloyloxy phenylethyl)-2-phenyloxetane, 2-(acryloyloxyethyl)-3-phenyloxetane, 2-(acryloyloxyethyl)-4-benzene oxetane, 2,3-difluoro-2-(acryloyloxyethyl)oxetane, 2,4-difluoro-2-(acryloyloxyethyl)oxy Hetidine, 3,3-difluoro-2-(acryloyloxyethyl)oxetane, 3,4-difluoro-2-(acryloyloxyethyl)oxetane Butane, 4,4-difluoro-2-(acryloyloxyethyl)oxetane, 2-(acryloyloxyethyl)-3,3,4-trifluorooxetane Butane, 2-(acryloyloxyethyl)-3,4,4-trifluorooxetane, 2-(acryloyloxyethyl)-3,3,4,4-tetrafluoro Acrylates such as oxetane.

Among them, in terms of the wide process range of the obtained photosensitive resin composition and the ability to improve the chemical corrosion resistance of the obtained protrusions and spacers, glycidyl methacrylate is preferably used as an unsaturated compound containing an epoxy group. , 2-methyl glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinyl Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether; as the unsaturated compound containing oxetanyl, it is preferable to use 3-(methacryloyloxymethyl)oxetane, 3- (Methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methyl 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 3-(methacryloyloxymethyl) )-3-ethyloxetane, 3-(methacryloyloxymethyl)-3-methyloxetane, 3-(acryloyloxymethyl)-3-ethyl Oxetane, 3-(acryloyloxymethyl)-3-methyloxetane and the like. They can be used alone or in combination.

The copolymer [A] used in the present invention preferably contains 10 to 80% by weight of the structural unit derived from the compound (a3), particularly preferably 20 to 70% by weight. When the constituent unit is less than 10% by weight, the storage stability of the copolymer [A] tends to decrease, and on the other hand, if it exceeds 80% by weight, the copolymer [A] is hardly soluble in an alkaline aqueous solution.

Examples of the compound (a3) include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate, and acrylic acid Alkyl acrylates such as methyl ester and isopropyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 ^2.6 ]dec-8-yl methacrylate ( As commonly used names in this field, methacrylate rings such as dicyclopentyl methacrylate, dicyclopentyloxyethyl methacrylate, isophorone methacrylate, etc. Alkyl esters, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2.6 ]dec-8-yl acrylate (as commonly used names in this field, also known as dicycloacrylate Cyclic alkyl acrylates such as dicyclopentyloxyethyl acrylate and isophorone acrylate, aryl methacrylates such as phenyl methacrylate and benzyl methacrylate , aryl acrylates such as phenyl acrylate and benzyl acrylate, dibasic carboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate, 2-hydroxyethyl methacrylate Hydroxyalkyl esters such as base esters and 2-hydroxypropyl methacrylate;

Bicyclo[2.2.1]hept-2-ene,

5-Methylbicyclo[2.2.1]hept-2-ene,

5-Ethylbicyclo[2.2.1]hept-2-ene,

5-Hydroxybicyclo[2.2.1]hept-2-ene,

5-carboxybicyclo[2.2.1]hept-2-ene,

5-Hydroxymethylbicyclo[2.2.1]hept-2-ene,

5-(2'-Hydroxyethyl)bicyclo[2.2.1]hept-2-ene,

5-methoxybicyclo[2.2.1]hept-2-ene,

5-Ethoxybicyclo[2.2.1]hept-2-ene,

5,6-Dihydroxybicyclo[2.2.1]hept-2-ene,

5,6-dicarboxybicyclo[2.2.1]hept-2-ene,

5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene,

5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene,

5,6-dimethoxybicyclo[2.2.1]hept-2-ene,

5,6-diethoxybicyclo[2.2.1]hept-2-ene,

5-Hydroxy-5-methylbicyclo[2.2.1]hept-2-ene,

5-Hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene,

5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene,

5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene,

5-Hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene,

5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene,

5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene,

5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (norbornene diacid anhydride),

5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene,

5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene,

5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene,

5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene,

5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds;

Phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimide N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleimide propionate Esters, N-(9-acridyl)maleimide and other dicarbonyl imide derivatives;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloride Ethylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, methyl Glycidyl acrylate, α-glycidyl ethacrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid- 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethacrylate , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.

Among them, styrene, tert-butyl methacrylate, dicyclopentyl methacrylate, p-methoxystyrene, 2-methyl acrylate are preferred from the viewpoint of copolymerization reactivity and solubility in alkaline aqueous solution Cyclohexyl ester, 1,3-butadiene, glycidyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Phenylmaleimide, cyclohexylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. These can be used alone or in combination.

As mentioned above, the copolymer [A] used in the present invention has a carboxyl group and/or a carboxylic acid anhydride group and an oxetanyl group, has appropriate solubility in an alkaline aqueous solution, and can be used without a specific curing agent. Cures easily by heating.

The radiation-sensitive resin composition containing the above-mentioned copolymer [A] does not cause development residue and film reduction during development, and easily forms a coating film with a predetermined pattern.

As a solvent used in synthesizing the copolymer [A], for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, etc. Ethers; methyl cellosolve acetate, ethyl cellosolve acetate and other glycol alkyl ether acetates; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Diethylene glycol such as dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; propylene glycol monoalkanes such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and other propylene glycol alkyl ether acetates; propylene glycol methyl ether propionic acid Ester, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and other propylene glycol alkyl ether propionates; aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy -Methyl 2-methylpropionate, 2-Hydroxy-2-methylpropionate ethyl, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, Butyl Lactate, Methyl 3-Hydroxypropionate, Ethyl 3-Hydroxypropionate, Propyl 3-Hydroxypropionate, Butyl 3-Hydroxypropionate, Methyl 2-Hydroxy-3-Methylbutyrate, Formaldehyde Methyl oxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, butoxy Propyl acetate, butoxybutyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate , Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Propyl 2-ethoxypropionate, Butyl 2-ethoxypropionate, Methyl 2-butoxypropionate , Ethyl 2-butoxypropionate, Propyl 2-butoxypropionate, Butyl 2-butoxypropionate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate , Propyl 3-methoxypropionate, Butyl 3-methoxypropionate, Methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, Propyl 3-ethoxypropionate , butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate , Methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate and other esters.

In addition, as the polymerization initiator used in the manufacture of the copolymer [A], a known radical polymerization initiator can be used, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-isobutyronitrile, Azo compounds such as azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide peroxide, organic peroxides such as lauroyl peroxide, tert-butylperoxypivalate, 1,1'-di-(tert-butylperoxy)cyclohexane, and hydrogen peroxide. When using a peroxide as a radical polymerization initiator, it is also possible to use a peroxide together with a reducing agent as an oxidation-reduction type initiator.

In the production of the copolymer [A], a molecular weight modifier for adjusting the molecular weight can be used. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide, n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, mercaptoethanol Thiols such as acids, xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide, terpinolene, α-methylstyrene dimer, etc.

The polystyrene-equivalent weight-average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] used in the present invention is usually 2×10 ³ to 5×10 ⁵ , preferably 5×10 ³ to 1× 10 ⁵ . If Mw is less than 2×10 ³ , the remaining film rate after development tends to decrease, and if it exceeds 5×10 ⁵ , development residue will occur.

Photocationic polymerization initiator[B]

Examples of the photocationic polymerization initiator [B] include onium salts. Onium salts are composed of onium cations and anions from Lewis acids.

Specific examples of the aforementioned onium cations include diphenyliodonium, bis(p-tolyl)iodonium, bis(p-tert-butylphenyl)iodonium, bis(p-octylphenyl)iodonium, Di(p-octadecylphenyl)iodonium, bis(p-octyloxyphenyl)iodonium, bis(p-octadecyloxyphenyl)iodonium, phenyl(p-octadecyl Oxyphenyl)iodonium, (p-tolyl)(p-isopropylphenyl)iodonium, methylnaphthyliodonium, ethylnaphthyliodonium, triphenylsulfonium, tris(p-toluene Base) sulfonium, three (p-isopropylphenyl) sulfonium, three (2,6-dimethylphenyl) sulfonium, three (p-tert-butylphenyl) sulfonium, three (p-cyanophenyl) )sulfonium, tri(p-chlorophenyl)sulfonium, dimethylnaphthylsulfonium, diethylnaphthylsulfonium, dimethyl(methoxy)sulfonium, dimethyl(ethoxy)sulfonium, dimethyl Dimethyl(butoxy)sulfonium, Dimethyl(butoxy)sulfonium, Dimethyl(octyloxy)sulfonium, Dimethyl(octadecyloxy)sulfonium, Dimethyl(isopropoxy)sulfonium , Dimethyl(tert-butoxy)sulfonium, Dimethyl(cyclopentyloxy)sulfonium, Dimethyl(cyclohexyloxy)sulfonium, Dimethyl(fluoromethoxy)sulfonium, Dimethyl( 2-chloroethoxy)sulfonium, dimethyl(3-bromopropoxy)sulfonium, dimethyl(4-cyanobutoxy)sulfonium, dimethyl(8-nitrooctyloxy) Sulfonium, Dimethyl(18-trifluoromethyloctadecyloxy)sulfonium, Dimethyl(2-hydroxyisopropoxy)sulfonium, Dimethyl(tri(trichloromethyl)methyl)sulfonium, etc. . Preferred are bis(p-tolyl)iodonium, (p-tolyl)(p-isopropylphenyl)iodonium, bis(p-tert-butylphenyl)iodonium, triphenylsulfonium, triphenylsulfonium, (p-tert-butylphenyl)sulfonium, etc.

Specific examples of the aforementioned anion derived from a Lewis acid include hexafluorophosphate, hexafluoroaluminate, hexafluoroantimonate, tetrakis(pentafluorophenyl)borate, and the like, preferably hexafluoroantimonate. , Four (pentafluorophenyl) borate.

The aforementioned onium cations and anions derived from Lewis acids can be combined arbitrarily.

Specifically, examples of [B] photocationic polymerization initiators include diphenyliodonium hexafluorophosphate, bis(p-tolyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium Onium hexafluorophosphate, bis(p-octylphenyl)iodonium hexafluorophosphate, bis(p-octadecylphenyl)iodonium hexafluorophosphate, bis(p-octyloxyphenyl) Iodide hexafluorophosphate, bis(p-octadecyloxyphenyl)iodonium hexafluorophosphate, phenyl(p-octadecyloxyphenyl)iodonium hexafluorophosphate, (p-toluene base) (p-isopropylphenyl) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluorophosphate, ethylnaphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, (p-tolyl)sulfonium hexafluorophosphate, tris(p-isopropylphenyl)sulfonium hexafluorophosphate, tris(2,6-dimethylphenyl)sulfonium hexafluorophosphate, tris(p- tert-butylphenyl)sulfonium hexafluorophosphate, tris(p-cyanophenyl)sulfonium hexafluorophosphate, tris(p-chlorophenyl)sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate Phosphate, Diethylnaphthylsulfonium hexafluorophosphate, Dimethyl(methoxy)sulfonium hexafluorophosphate, Dimethyl(ethoxy)sulfonium hexafluorophosphate, Dimethyl(propoxy)sulfonium hexafluorophosphate Sulfonium hexafluorophosphate, Dimethyl(butoxy)sulfonium hexafluorophosphate, Dimethyl(octyloxy)sulfonium hexafluorophosphate, Dimethyl(octadecyloxy)sulfonium hexafluorophosphate, Dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclo Hexyloxy)sulfonium hexafluorophosphate, dimethyl(fluoromethoxy)sulfonium hexafluorophosphate, dimethyl(2-chloroethoxy)sulfonium hexafluorophosphate, dimethyl(3- Bromopropoxy)sulfonium hexafluorophosphate, dimethyl(4-cyanobutoxy)sulfonium hexafluorophosphate, dimethyl(8-nitrooctyloxy)sulfonium hexafluorophosphate, dimethyl Dimethyl(18-trifluoromethyloctadecyloxy)sulfonium hexafluorophosphate, dimethyl(2-hydroxyisopropoxy)sulfonium hexafluorophosphate, dimethyl(tris(trichloromethyl)formazolium base) sulfonium hexafluorophosphate;

Diphenyliodonium hexafluoroaluminate, bis(p-tolyl)iodonium hexafluoroaluminate, bis(p-tert-butylphenyl)iodonium hexafluoroaluminate, bis(p-octylbenzene base) iodonium hexafluoroaluminate, bis(p-octadecylphenyl)iodonium hexafluoroaluminate, bis(p-octyloxyphenyl)iodonium hexafluoroaluminate, bis(p- -octadecyloxyphenyl)iodonium hexafluoroaluminate, phenyl(p-octadecyloxyphenyl)iodonium hexafluoroaluminate, (p-tolyl)(p-isopropyl Phenyl)iodonium hexafluoroaluminate, methylnaphthyliodonium hexafluoroaluminate, ethylnaphthyliodonium hexafluoroaluminate, triphenylsulfonium hexafluoroaluminate, tris(p-toluene Base) sulfonium hexafluoroaluminate, tris (p-isopropylphenyl) sulfonium hexafluoroaluminate, tris (2,6-dimethylphenyl) sulfonium hexafluoroaluminate, tris (p-tert Butylphenyl)sulfonium hexafluoroaluminate, tris(p-cyanophenyl)sulfonium hexafluoroaluminate, tris(p-chlorophenyl)sulfonium hexafluoroaluminate, dimethylnaphthylsulfonium Hexafluoroaluminate, diethylnaphthylsulfonium hexafluoroaluminate, dimethyl(methoxy)sulfonium hexafluoroaluminate, dimethyl(ethoxy)sulfonium hexafluoroaluminate, dimethyl (propoxy)sulfonium hexafluoroaluminate, dimethyl(butoxy)sulfonium hexafluoroaluminate, dimethyl(octyloxy)sulfonium hexafluoroaluminate, dimethyl(octadecane oxy)sulfonium hexafluoroaluminate, dimethyl(isopropoxy)sulfonium hexafluoroaluminate, dimethyl(tert-butoxy)sulfonium hexafluoroaluminate, dimethyl(cyclopentyloxy ) sulfonium hexafluoroaluminate, dimethyl (cyclohexyloxy) sulfonium hexafluoroaluminate, dimethyl (fluoromethoxy) sulfonium hexafluoroaluminate, dimethyl (2-chloroethyl oxy)sulfonium hexafluoroaluminate, dimethyl(3-bromopropoxy)sulfonium hexafluoroaluminate, dimethyl(4-cyanobutoxy)sulfonium hexafluoroaluminate, dimethyl (8-nitrooctyloxy)sulfonium hexafluoroaluminate, dimethyl(18-trifluoromethyloctadecyloxy)sulfonium hexafluoroaluminate, dimethyl(2-hydroxyisopropoxy base) sulfonium hexafluoroaluminate, dimethyl (tris(trichloromethyl)methyl) sulfonium hexafluoroaluminate;

Diphenyliodonium hexafluoroantimonate, bis(p-tolyl)iodonium hexafluoroantimonate, bis(p-tert-butylphenyl)iodonium hexafluoroantimonate, bis(p-octylbenzene Base) iodonium hexafluoroantimonate, bis(p-octadecylphenyl)iodonium hexafluoroantimonate, bis(p-octyloxyphenyl)iodonium hexafluoroantimonate, bis(p- -octadecyloxyphenyl)iodonium hexafluoroantimonate, phenyl(p-octadecyloxyphenyl)iodonium hexafluoroantimonate, (p-tolyl)(p-isopropyl Phenyl)iodonium hexafluoroantimonate, methylnaphthyliodonium hexafluoroantimonate, ethylnaphthyliodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tri(p-toluene Base) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris (2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert Butylphenyl)sulfonium hexafluoroantimonate, tris(p-cyanophenyl)sulfonium hexafluoroantimonate, tris(p-chlorophenyl)sulfonium hexafluoroantimonate, dimethylnaphthylsulfonium Hexafluoroantimonate, diethylnaphthylsulfonium hexafluoroantimonate, dimethyl(methoxy)sulfonium hexafluoroantimonate, dimethyl(ethoxy)sulfonium hexafluoroantimonate, dimethyl Base (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl (octadecyl) Oxygen)sulfonium hexafluoroantimonate, dimethyl(isopropoxy)sulfonium hexafluoroantimonate, dimethyl(tert-butoxy)sulfonium hexafluoroantimonate, dimethyl(cyclopentyloxy) ) sulfonium hexafluoroantimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethyl Oxy)sulfonium hexafluoroantimonate, dimethyl(3-bromopropoxy)sulfonium hexafluoroantimonate, dimethyl(4-cyanobutoxy)sulfonium hexafluoroantimonate, dimethyl Dimethyl(8-nitrooctyloxy)sulfonium hexafluoroantimonate, dimethyl(18-trifluoromethyloctadecyloxy)sulfonium hexafluoroantimonate, dimethyl(2-hydroxyisopropoxy Base) sulfonium hexafluoroantimonate, dimethyl (tris(trichloromethyl)methyl) sulfonium hexafluoroantimonate;

Diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(p-tolyl)iodonium tetrakis(pentafluorophenyl)borate, bis(p-tert-butylphenyl)iodonium tetrakis(pentafluorophenyl)borate Fluorophenyl) borate, bis(p-octylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(p-octadecylphenyl)iodonium tetrakis(pentafluorophenyl) Borate, bis(p-octyloxyphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(p-octadecyloxyphenyl)iodoniumtetrakis(pentafluorophenyl)boronic acid salt, phenyl(p-octadecyloxyphenyl)iodonium tetrakis(pentafluorophenyl) borate, (p-tolyl)(p-isopropylphenyl)iodonium tetrakis(pentafluorophenyl) base) borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate ) borate, tris(p-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, tris(p-isopropylphenyl)sulfonium tetrakis(pentafluorophenyl)borate, tris(2, 6-Dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate, tris(p-tert-butylphenyl)sulfonium tetrakis(pentafluorophenyl)borate, tris(p-cyanophenyl) )sulfonium tetrakis(pentafluorophenyl)borate, tris(p-chlorophenyl)sulfonium tetrakis(pentafluorophenyl)borate, dimethylnaphthylsulfonium tetrakis(pentafluorophenyl)borate , Diethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate Fluorophenyl) borate, dimethyl(propoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(butoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl Dimethyl(octyloxy)sulfonium tetrakis(pentafluorophenyl)borate, Dimethyl(octadecyloxy)sulfonium tetrakis(pentafluorophenyl)borate, Dimethyl(isopropoxy)sulfonium Tetrakis(pentafluorophenyl)borate, Dimethyl(tert-butoxy)sulfonium tetrakis(pentafluorophenyl)borate, Dimethyl(cyclopentyloxy)sulfonium tetrakis(pentafluorophenyl)boron Dimethyl(cyclohexyloxy)sulfonium tetrakis(pentafluorophenyl)borate, Dimethyl(fluoromethoxy)sulfonium tetrakis(pentafluorophenyl)borate, Dimethyl( 2-Chloroethoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(3-bromopropoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(4- Cyanobutoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(8-nitrooctyloxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(18-trifluorophenyl) Methyloctadecyloxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(2-hydroxyisopropoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(tri( Trichloromethyl)methyl)sulfonium tetrakis(pentafluorophenyl)borate and the like.

Preferred are bis(p-tolyl)iodonium hexafluorophosphate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluorophosphate, di(p-tert-butylphenyl)iodonium Onium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris(p-tert-butylphenyl)sulfonium hexafluorophosphate, bis(p-tolyl)iodonium hexafluoroaluminate, (p-toluene base) (p-isopropylphenyl) iodonium hexafluoroaluminate, bis(p-tert-butylphenyl) iodonium hexafluoroaluminate, triphenylsulfonium hexafluoroaluminate, tris(p- tert-butylphenyl)sulfonium hexafluoroaluminate, bis(p-tolyl)iodonium hexafluoroantimonate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluoroantimonate , Di(p-tert-butylphenyl)iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tri(p-tert-butylphenyl)sulfonium hexafluoroantimonate, bis(p- Tolyl)iodonium tetrakis(pentafluorophenyl)borate, (p-tolyl)(p-isopropylphenyl)iodoniumtetrakis(pentafluorophenyl)borate, bis(p-tert-butyl phenyl)iodonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, tris(p-tert-butylphenyl)sulfonium tetrakis(pentafluorophenyl) Borate etc.

More preferred are bis(p-tolyl)iodonium hexafluoroantimonate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluoroantimonate, bis(p-tert-butylbenzene base) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris(p-tert-butylphenyl)sulfonium hexafluoroantimonate, di(p-tolyl)iodonium tetrakis(pentafluoro Phenyl)borate, (p-tolyl)(p-isopropylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(p-tert-butylphenyl)iodonium tetrakis(pentafluorophenyl) Fluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like.

The usage ratio of [B] component is 0.01-15 weight part with respect to 100 weight part of copolymer [A], Preferably it is 0.1-10 weight part. Based on the aforementioned standard, if the amount is 0.01 to 15 parts by weight, the curing speed of the exposed part can be increased, the reduction of the film of the pattern during development can be suppressed, and the remaining film rate can be increased, so it is preferable.

Thioxanthones[C]

Examples of [C] thioxanthone compounds include thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,3-diethylthioxanthone, 2,4 - Diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-cyclohexylthioxanthone, 4-cyclohexylthioxanthone and the like.

The proportion of component [C] used is usually 15 parts by weight or less, preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the copolymer [A]. [C] When the content of the component is 0.01 to 15 parts by weight, it can sensitize the photocationic polymerization initiator, increase the curing speed during curing, suppress the decrease in resolution during curing, and further improve the solvent resistance of the cured film, so it is preferred.

other ingredients

The radiation-sensitive resin composition of the present invention contains the above-mentioned copolymers [A] and [B] components, or [C] component as an essential component, and may further contain [D] crosslinking agent, [E] polymerizable monomer as necessary , [F] surfactant or [G] adhesion promoter.

The above [D] crosslinking agent is a component that forms a crosslinked structure between molecules of the specific alkali-soluble resin that is the [A] component. As such a crosslinking agent, a condensation product of urea and formaldehyde (hereinafter referred to as "urea-formaldehyde condensation product"), a condensation product of melamine and formaldehyde (hereinafter referred to as "melamine-formaldehyde condensation product"), Methylol urea alkyl ethers and methylol melamine alkyl ethers obtained from these condensation products and alcohols.

Specific examples of the aforementioned urea-formaldehyde condensation products include monomethylol urea, dimethylol urea, and the like.

As a specific example of the aforementioned melamine-formaldehyde condensation product, hexamethylol melamine can be mentioned, and a product of partial condensation of melamine and formaldehyde can also be used.

The aforementioned methylol urea alkyl ethers are obtained by reacting a part or all of the methylol groups in the urea-formaldehyde condensation product with alcohol, and specific examples thereof include monomethylol urea methyl ether, dimethylol Base urea methyl ether, etc.

The above-mentioned methylolmelamine alkyl ethers are obtained by reacting part or all of the methylol groups of the melamine-formaldehyde condensation product with alcohols such as methanol and n-butanol, and specific examples thereof include hexamethylolmelamine hexamethylol Methyl ether, hexamethylolmelamine hexa-n-butyl ether, a compound having a structure in which the hydrogen atom of the amino group of melamine is substituted with methylol and methoxymethyl groups, and the hydrogen atom of the amino group of melamine is replaced with butoxymethyl Group and methoxymethyl substituted structure compounds, etc.

Among them, methylolmelamine alkyl ethers are preferably used, and commercially available products of such methylolmelamine alkyl ethers include "Symel 300", "Symel 370", "Symel 232" manufactured by Mitsui Cytec Co., Ltd. ", "マイコ一ト505" and so on.

The proportion of the [D] crosslinking agent used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the component [A].

When the ratio exceeds 50 parts by weight, the thickness of the portion of the coating film that is not irradiated with radiation is remarkably reduced during the development treatment, and the transparency of the resulting coating film is also reduced.

As the [E] polymerizable monomer, for example, a thermally radical polymerizable monomer, a cationically polymerizable polymerizable monomer, and the like can be used.

Examples of polymerizable monomers that can be radically polymerized include compounds having polymerizable carbon-carbon unsaturated bonds, which may be monofunctional polymerizable monomers, difunctional polymerizable monomers, trifunctional or Polyfunctional polymerizable monomers such as more functional polymerizable monomers.

Examples of monofunctional polymerizable monomers include nonylphenyl carbitol acrylate, nonylphenyl carbitol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, methyl 2-Hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate, 2-hydroxyethyl acrylate, methacrylic acid 2-hydroxyethyl ester, N-vinylpyrrolidone, etc.

Examples of bifunctional polymerizable monomers include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethyl Acrylates, Neopentyl Glycol Diacrylate, Neopentyl Glycol Dimethacrylate, Triethylene Glycol Diacrylate, Triethylene Glycol Dimethacrylate, Bis(acryloyloxyethyl) of Bisphenol A Ether, 3-methylpentanediol diacrylate, 3-methylpentanediol dimethacrylate, etc.

Examples of the trimethylolpropane trimethacrylate or more trifunctional polymerizable monomer include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and pentaerythritol tetraacrylate. ester, pentaerythritol tetramethacrylate, pentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. Among the aforementioned polymerizable monomers, difunctional or trifunctional or more polymerizable monomers are preferably used. Specifically, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. are preferable, and dipentaerythritol hexaacrylate is more preferable. In addition, a difunctional or trifunctional or more polymerizable monomer may be used together with a monofunctional polymerizable monomer.

Examples of the cationically polymerizable polymerizable monomer include polymerizable monomers having cationically polymerizable functional groups such as vinyl ether groups, propenyl ether groups, epoxy groups, and oxetanyl groups. Specifically, examples of vinyl ether group-containing compounds include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl Vinyl ether and the like; as a compound containing a propenyl ether group, 4-(1-propenyloxymethyl)-1,3-dioxolane-2-one, etc.; as a compound containing an epoxy group , can include bisphenol A type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type cyclic Oxygen resin, heterocyclic epoxy resin; As the compound containing oxetanyl, bis{3-(3-ethyloxetanyl) methyl} ether, 1,4-bis{3 -(3-Ethyloxetanyl)methoxy}benzene, 1,4-bis{3-(3-ethyloxetanyl)methoxy}toluene, 1,4-bis{3 -(3-Ethyloxetanyl)methoxy}cyclohexane, 1,4-bis{3-(3-ethyloxetanyl)methoxy}methylcyclohexane, 3 -(3-Ethyloxetanyl)methylated novolac resin, etc.

When the aforementioned polymerizable monomers are used, they may be used alone or in combination. The addition amount of the [E] polymerizable monomer in the radiation-sensitive resin composition of the present invention is preferably 30 parts by weight or less based on 100 parts by weight of the copolymer [A].

The above-mentioned [F] surfactant can be used in the radiation-sensitive resin composition of the present invention to further improve coatability. As the [F] surfactant used here, fluorosurfactants, silicone-based surfactants and nonionic surfactants can be used.

Specific examples of fluorosurfactants include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl Hexyl ether, octaethylene glycol bis (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octaethylene glycol Propylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate , 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, and fluoroalkylbenzene Sodium sulfonates, fluoroalkyloxyethylene ethers, fluoroalkylammonium iodides, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethanols, perfluoroalkyl alkoxides , Fluoroalkyl esters, etc. In addition, examples of these commercially available products include BM-1000, BM-1100 (manufactured by BM Chemie), Megafact F142D, Megafact F172, Megafact F173, Megafact F183, Megafact F178, Megafact F191, Megafact F471 (above, Dainippon Ink Chemicals Co., Ltd.), Fluoride FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo Triem Co., Ltd.), Surflon S-112, Surflon Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon Fron SC-103, Surfron SC-104, Surfron SC-105, Surfron SC-106 (above, manufactured by Asahi Glass Co., Ltd.), Eftop EF301, Eftop EF 303, Eftop EF 352 (above, Shin Akita Kasei Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (Toray Silicon Co., Ltd.) and the like.

In addition, examples of silicone-based surfactants include Toresilicone DC3PA, Toresilicone DC7PA, Toresilicone SH11PA, Toresilicone SH21PA, Toresilicone SH28PA, and Toresilicone SH28PA.一レシリコン SH29PA, トレシリコン SH30PA, トレシリコン FS-1265-300 (manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF Products sold under trade names such as -4445, TSF-4446, TSF-4460, and TSF-4452 (above, manufactured by GE Toshiba Silicon Co., Ltd.).

As the above-mentioned nonionic surfactant, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene octylphenyl Polyoxyethylene aryl ethers such as ether and polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, etc., and (methyl ) acrylic copolymer Polyflor-1 No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

These surfactants can be used alone or in combination of two or more.

The surfactant [F] is preferably used in an amount of 5 parts by weight or less, more preferably in an amount of 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. At this time, if the amount of the surfactant [F] exceeds 5 parts by weight, when the coating film is formed on the substrate, the coating film tends to be rough.

Moreover, in order to further improve the adhesiveness with a board|substrate, you may mix an adhesive auxiliary [G] with the radiation-sensitive resin composition of this invention.

As such an adhesion aid [G], it is preferable to use a functional silane coupling agent, and examples thereof include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyl Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. The compounding amount of such an adhesion aid [G] is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, relative to 100 parts by weight of the copolymer [A]. When the amount of the adhesion assistant exceeds 20 parts by weight, an afterimage after image development is likely to occur in the image development step.

Radiation sensitive resin composition

The radiation-sensitive resin composition of the present invention can be prepared by uniformly mixing the above-mentioned copolymer [A], [B] components, and other components arbitrarily added as above. Usually, the radiation resin composition of the present invention is dissolved in an appropriate solvent and used in a solution state. For example, a radiation-sensitive resin composition in a solution state is prepared by mixing the copolymers [A], [B] components, and other components optionally added in a predetermined ratio.

As the solvent used in the preparation of the radiation-sensitive resin composition of the present invention, various components that can uniformly dissolve the components [A] and [B] of the copolymer and other components optionally added, and that do not react with each component can be used. solvent.

Examples of such a solvent include the same solvents as those exemplified when producing the above-mentioned copolymer [A].

Among these solvents, glycol ethers, glycol alkyl ether acetates, esters, and diethylene glycol are preferably used from the viewpoint of the solubility of each component, the reactivity with each component, and the ease of coating film formation. kind. Among them, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate, and ethoxy propionate are particularly preferably used. ethyl ester.

When preparing the radiation-sensitive resin composition of the present invention in a solution state, the ratio of components other than the solvent in the solution (that is, the total amount of the copolymer [A], [B] components and other components optionally added) can be It is arbitrarily set according to the purpose of use, the desired film thickness, etc., and is usually 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 15 to 35% by weight.

The composition solution prepared in this way is used after filtration with a microporous filter having a pore diameter of about 0.2 μm or the like.

Formation of protrusions and/or dividers

Next, a method of forming the protrusions and/or partitions of the present invention using the radiation-sensitive resin composition of the present invention will be described. The method for forming protrusions and/or partitions of the present invention includes at least the following steps.

(1) A step of forming a coating film of the radiation-sensitive resin composition of the present invention on a substrate.

(2) A step of irradiating radiation to at least a part of the coating film.

(3) Developing process.

(4) Heating process.

(1) Step of forming a coating film of the radiation-sensitive resin composition of the present invention on a substrate

In the step (1) above, the composition solution of the present invention is coated on the surface of the substrate, and the solvent is prebaked to remove the solvent to form a coating film of the radiation-sensitive resin composition.

The types of substrates used in the present invention include glass substrates, silicon wafers, and substrates formed with various metals on their surfaces.

As a method of forming the photosensitive resin composition coating film of this invention, (1) coating method and (2) dry film method can be employ|adopted, for example.

As the coating method of the composition solution, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method, a bar coating method, or an inkjet coating method can be used. , particularly preferably a spin coating method or a slit coating method.

In addition, when the coating film of the photosensitive resin composition of the present invention is formed by the (2) dry film method, the dry film is laminated with the photosensitive resin of the present invention on a base film, preferably a flexible base film. A photosensitive layer formed from the composition (hereinafter referred to as "photosensitive dry film").

The photosensitive dry film is formed by coating the photosensitive resin composition of the present invention, preferably a liquid composition, on a base film, drying, and laminating a photosensitive layer. As the base film of the photosensitive dry film, for example, synthetic resin films such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, and polyvinyl chloride can be used. The thickness of the base film is suitably 15 to 125 μm. The thickness of the obtained photosensitive layer is preferably about 1 to 30 μm.

In addition, when the photosensitive dry film is not in use, a protective film can be further laminated on the photosensitive layer and stored. The protective film does not peel off when not in use, but can be easily peeled off when in use, so it must have appropriate mold release properties. Examples of protective films satisfying these conditions include films formed by coating or firing a silicone-based release agent on the surface of synthetic resins such as PET films, polypropylene films, polyethylene films, and polyvinyl chloride films. The thickness of the protective film is generally about 25 μm. Conditions for the pre-baking vary depending on the type, usage ratio, and the like of each component. For example, it may be performed at 60 to 110° C. for about 30 seconds to 15 minutes.

(2) Step of irradiating at least a part of the coating film with radiation

In the step (2) above, radiation is irradiated through a mask having a predetermined pattern, and then the radiation-irradiated portion is removed by developing using a developer, and patterned on the formed coating film. Examples of the radiation used at this time include ultraviolet rays, extreme ultraviolet rays, X-rays, charged particle beams, and the like.

As said ultraviolet-ray, g-line (wavelength 436 nm), i-line (wavelength 365 nm), etc. are mentioned, for example. As far ultraviolet rays, KrF excimer laser etc. are mentioned, for example. Examples of X-rays include synchrotron radiation and the like. As a charged particle beam, an electron beam etc. are mentioned, for example.

Among them, ultraviolet rays are preferable, and radiation containing g-rays and/or i-rays is particularly preferable.

As the pattern mask used for exposure and the exposure operation may be: (1) a method of using one photomask having two patterns of a protrusion part and a spacer part, and a single exposure (the position where the part of the mask is smaller, The effect of transmitted light cannot be ignored, and the height difference is formed according to the melt flow during baking); (2) Two types of photomasks with only protrusions and only spacers are used, and the process is performed twice method of exposure. In addition, as the pattern mask used in the method (1), a mask having different transmittances between the protrusion portion and the spacer portion may be used. However, in the present invention, depending on circumstances, only one of the protrusions and the spacers may be formed on the substrate. In this case, (3) a photomask with only the protrusions and a photomask with only the spacers can be used. Any type of photomask that performs a single exposure. In addition, in this case, protrusions and partitions which must remain in the vertical alignment type liquid crystal display element are formed by a conventionally known method.

(3) Development process

As a developing solution used in the developing process, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazepine Aqueous solutions of bases such as heterobicyclo[5,4,0]-7-undecene and 1,5-diazabicyclo[4,3,0]-5-nonane. In addition, water-soluble organic solvents such as methanol and ethanol and surfactants can be appropriately added to the above-mentioned alkaline aqueous solution to form an aqueous solution, and various organic solvents that form an aqueous solution or dissolve the composition of the present invention are used as a developer. In addition, as a developing method, appropriate methods such as a soaking method, a dipping method, a shaking dipping method, and a shower method may be used. The developing time at this time varies depending on the composition of the composition, but is usually about 30 to 180 seconds.

(4) Heating process

After the above-mentioned (3) developing step, it is preferable to perform a shower treatment based on running water washing to the patterned film, and it is more preferable to irradiate the whole surface with radiation (post-exposure) by a high-pressure mercury lamp or the like to remove the remaining 1,2- After the quinonediazide compound is decomposed, the film is subjected to heat treatment (post-baking treatment) by a heating device such as a hot plate or an oven, and the film is cured. The exposure amount in the post-exposure step is preferably about 2,000 to 5,000 J/m ² . In addition, the firing temperature of this curing treatment is, for example, 120 to 250° C., and the heating time varies depending on the type of heater. For example, when heat treatment is performed on a hot plate, it is 5 to 30 minutes, and when heat treatment is performed in an oven , is 30-90 minutes. At this time, a step baking method in which two or more heating steps are performed may also be used.

In this manner, a patterned thin film corresponding to the desired protrusions and/or partitions can be formed on the surface of the substrate.

The height of the protrusions thus formed is usually 0.1-3.0 μm, preferably 0.5-2.0 μm, particularly preferably 1.0-1.5 μm; and the height of the partition is usually 1-10 μm, preferably 2-8 μm, particularly preferably 3-10 μm. 5 μm.

According to the method of forming the protrusions and/or partitions used in the vertical alignment type liquid crystal display element of the present invention, fine processing is possible, and the shape and size (height and bottom size) can be easily controlled, and the pattern shape can be stably and productively formed. , heat resistance, solvent resistance, transparency, etc. fine protrusions and partitions, and can also provide a vertical alignment type liquid crystal display element excellent in orientation, voltage retention, etc.

[Example]

Hereinafter, the present invention will be described more specifically by showing synthesis examples and examples, but the present invention is not limited to these examples.

Synthesis example of copolymer [A]

Synthesis Example 1

In the flask with cooling tube and stirrer, add 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile), 200 parts by weight of diethylene glycol methyl ethyl ether, and then add 18 Parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, 32 parts by weight of tricyclo[5.2.1.0 ^2.6 ]decane-8-yl methacrylate, after nitrogen replacement, add 5 parts by weight 1,3-butadiene, the temperature of the solution was raised to 70° C. while stirring slowly, and the temperature was kept at this temperature for 5 hours for polymerization to obtain a solution of the copolymer [A-1].

The solid content concentration of this solution was 33.0% by weight, the Mw of the copolymer [A-1] was 11,000, and the molecular weight distribution (ratio of weight average molecular weight/number average molecular weight) was 1.8. In addition, a weight average molecular weight and a number average molecular weight are the average molecular weight of polystyrene conversion measured using GPC (gel permeation chromatography (HLC-8020 manufactured by Tosoh Co., Ltd.).

Synthesis example 2

Into a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate were charged. Then add 20 parts by weight styrene, 25 parts by weight methacrylic acid, 20 parts by weight phenylmaleimide, 35 parts by weight 3-(methacryloyloxymethyl)-3-ethyloxetane Alkanes, 1.5 parts of α-methylstyrene dimer, while nitrogen replacement, began to stir slowly. The temperature of the solution was raised to 70° C. and heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-2]. The solid content concentration of the obtained polymer solution was 31.0%, the weight average molecular weight of the polymer was 21,000, and the molecular weight distribution was 2.1.

Synthesis example 3

Into a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate were charged. Then, 28 parts by weight of styrene, 18 parts by weight of methacrylic acid, and 54 parts of 3-(methacryloyloxymethyl)-3-ethyloxetane were added, and slowly stirred while replacing nitrogen. The temperature of the solution was raised to 70° C. and heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-3]. The solid content concentration of the obtained polymer solution was 31.2%, the weight average molecular weight of the polymer was 23,000, and the molecular weight distribution was 2.6.

Example 1

[Preparation of Radiation Sensitive Resin Composition]

A solution containing the polymer [A-1] as the component [A] synthesized in Synthesis Example 1 above in an amount corresponding to 100 parts by weight of the polymer [A-1] (solid content), and 3 parts by weight as the component [ B] two (p-tolyl) iodonium hexafluoroantimonate (B-1) mixed, dissolved in diethylene glycol ethyl methyl ether, after making the solid content concentration 30% by weight, use a diameter of 0.2 Filter through a μm membrane filter to prepare a radiation-sensitive resin composition solution (S-1).

Embodiment 2-4

Except that in Example 1, the types and amounts of the [A] component, [B] component, and [C] component described in Table 1 were used, the same treatment as in Example 1 was carried out to prepare the radiation-sensitive resin composition. Solutions (S-2) to (S-4).

In addition, the abbreviations of the components in Table 1 represent the following compounds.

(B-1): Bis(p-tolyl)iodonium hexafluoroantimonate

(B-2): (p-tolyl)(p-isopropylphenyl) iodide tetrakis (pentafluorophenyl) borate [Rhodorsil Photoinitiator 2074 (manufactured by Rodia Corporation)]

(C-1): 2,4-Dimethylthioxanthone

【Table 1】 Composition name Copolymer [A] [B] Ingredients [C] Ingredients type Quantity (parts by weight) type Quantity (parts by weight) type Quantity (parts by weight) Example 1 (S-1) [A-1] 100 [B-1] 3 Example 2 (S-2) [A-2] 100 [B-2] 3 Example 3 (S-3) [A-3] 100 [B-1] 2.5 Example 4 (S-4) [A-1] 100 [B-1] 3 [C-1] 2

Using the radiation-sensitive resin composition prepared as above, protrusions and partitions were formed as follows, and various properties were evaluated.

[Protrusion and partition formation]

After coating the above-mentioned composition on a silicon substrate with a spinner, it was prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with a film thickness of 4.0 μm. After that, pass through a photomask having a remaining 5 μm wide pattern corresponding to the protrusion portion and a dot pattern corresponding to the remaining 30 μm of the spacer portion, and pass through a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Cannon Co., Ltd., Expose by changing the exposure time. Thereafter, after developing for 100 seconds with the type of developer at 25° C., developer concentration, and developing method described in the table, the wafer was washed with pure water for 1 minute and dried to form a pattern on the wafer. The amount of exposure required for forming a pattern corresponding to the remaining 5 μm width of the protrusion portion and a pattern of dots corresponding to the remaining 30 μm of the spacer portion was measured. This value is regarded as a sensitivity, and is shown in a table. When this value is 3500J/m ² or below, it can be said that the sensitivity is good.

[Evaluation of cross-sectional shape of protrusions]

When the cross-sectional shape A, B, or C of the protrusion is defined as follows, the cross-sectional shape of the formed protrusion was observed with a scanning electron microscope, and the case of A or B was "good", and the case of C was "poor". A, B, and C of the cross-sectional shapes of the protrusions are schematically illustrated in FIG. 1 .

A: When the bottom size is greater than 5 μm and less than or equal to 7 μm,

B: The case where the bottom size is larger than 7 μm,

C: The case of trapezoidal shape irrespective of the size of the bottom.

[Evaluation of the cross-sectional shape of the separator]

When the cross-sectional shape A, B, or C of the separator is defined as follows, the cross-sectional shape of the formed separator was observed with a scanning electron microscope, and the case of A or C was "good", and the case of C was "poor". A, B, and C of cross-sectional shapes of the separator are schematically illustrated in FIG. 1 .

A: When the bottom size is greater than 30 μm and less than or equal to 36 μm,

B: The case where the bottom size is larger than 36 μm,

C: The case of trapezoidal shape irrespective of the size of the bottom.

[Evaluation of solvent resistance]

After coating the composition on a silicon substrate with a spinner, it was prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with a film thickness of 3.0 μm. Thereafter, the obtained coating film was exposed at a cumulative irradiation dose of 3,000 J/m ² with a PLA-501F exposure machine (ultrahigh pressure mercury lamp) manufactured by Canon Co., Ltd. This silicon substrate was heated at 220° C. for 1 hour in a clean oven to obtain a cured film. The film thickness (T1) of the obtained cured film was measured. Then, after immersing the silicon substrate on which the cured film was formed in dimethyl sulfoxide whose temperature was controlled at 70°C for 20 minutes, the film thickness (t1) of the cured film was measured, and the film thickness change rate {|t1 due to immersion was calculated. -T1|/T1}×100(%). The results are shown in Table 2. When the value is 5% or less, the solvent resistance is considered to be good.

In addition, in the evaluation of solvent resistance, since it is not necessary to pattern the formed film, the radiation irradiation process and the development process can be omitted, and only the coating film formation process, post-baking process, and heating process can be used for evaluation.

[Evaluation of heat resistance]

A cured film was formed in the same manner as the above-mentioned solvent resistance evaluation, and the film thickness (T2) of the obtained cured film was measured. Then, after the cured film substrate was additionally baked at 240°C for 1 hour in a clean oven, the film thickness (t2) of the cured film was measured, and the film thickness change rate {|t2-T2| /T2}×100(%). The results are shown in Table 2. When the value is 5% or less, the heat resistance is considered to be good.

[Transparency evaluation]

In the said solvent resistance evaluation, the cured film was formed on the glass substrate similarly except having used the glass substrate "Corning 7059" (manufactured by Corning) instead of the silicon substrate. Using a spectrophotometer "Type 150-20 Daburbim (manufactured by Hitachi, Ltd.), measure the light transmittance of the glass substrate with the cured film at a wavelength of 400 to 800 nm. At this time, the lowest light transmittance The pass rate is shown in Table 2. When the value is 90% or more, the transparency is considered to be good.

[Evaluation of orientation and voltage retention]

Using the composition solution, protrusions and spacers were formed in the same manner as the above method on the electrode surface of a glass substrate having an ITO (tin-coated indium oxide) film as an electrode. After that, AL1H659 (trade name, manufactured by Geeise All Co., Ltd.) as a liquid crystal aligning agent was applied on the glass substrate on which protrusions and partitions were formed by using a printer for applying a liquid crystal aligning film, and dried at 180° C. for 1 hour. hours, a coating film with a film thickness of 0.05 μm is formed. In addition, AL1H659 as a liquid crystal aligning agent was coated on the electrode surface of another glass substrate having an ITO film with a printer for coating a liquid crystal aligning film, and dried at 180° C. for 1 hour to form a coating film with a film thickness of 0.05 μm. . Next, on the outer surface of each liquid crystal aligning film of the obtained two substrates, screen printing coating is added the epoxy resin adhesive of the glass fiber of diameter 5 μm, and the two substrates are pressed together so that the surfaces of the liquid crystal aligning films overlap relatively. , after which the adhesive is allowed to cure. After that, liquid crystal MLC-6608 (trade name) manufactured by Merck Co., Ltd. was filled between the two substrates through the liquid crystal injection port, and after the liquid crystal injection port was sealed with an epoxy-based adhesive, polarizing plates were attached to the outer surfaces of the two substrates, so that Its polarization direction is orthogonal to manufacture vertical alignment type liquid crystal display elements. In Fig. 2, a longitudinal cross-sectional view of the obtained vertical alignment type liquid crystal display element is schematically shown, wherein the reference numeral 1 represents a separator, the reference numeral 2 represents a protrusion, the reference numeral 3 represents a liquid crystal, the reference numeral 4 represents a liquid crystal alignment film, and the reference numeral 5 represents a color filter. Reference numeral 6 denotes a glass substrate.

Next, the orientation and voltage retention of the obtained vertical alignment type liquid crystal display element were evaluated as follows.

Orientation was evaluated by observing whether an abnormal region was generated in the liquid crystal cell with a polarizing microscope when the voltage was turned on and off, and when no abnormal region was confirmed, it was regarded as "good". In addition, when evaluating the voltage retention ratio, after applying 5V to the liquid crystal display element, the circuit was disconnected, and the retention voltage was measured 16.7 milliseconds later, and the ratio of the retention voltage to the applied voltage (5V) was calculated. When this value was 98% or more, it was considered good.

【Table 2】 composition type Developing method Developer Sensitivity evaluation Section shape Solvent resistance heat resistance Transparency (%) Orientation Voltage retention rate (%) Developer concentration (weight%) Sensitivity J/m ² protrusion divider Film thickness after curing (μm) Film thickness change rate (%) Film thickness after curing (μm) Film thickness change rate (%) Example 1 (S-1) liquid method TMAH 0.4 2800 A C 2.4 2 2.4 3 94 good 99.7 Example 2 (S-2) liquid method KOH 0.1 2500 A C 2.4 2 2.4 3 94 good 99.7 Example 3 (S-3) shower method TMHA 0.4 2200 A C 2.5 2 2.5 3 94 good 99.7 Example 4 (S-4) shower method TMAH 0.4 2800 A C 2.4 1 2.4 1 95 good 99.7

Claims (6)

1. radiation sensitive resin composition that is used to form employed projection of vertical alignment-type liquid crystal display device and/or separator is characterized in that: comprises,

The multipolymer that [A] obtains following (a1)～(a3) copolymerization, wherein (a1) is unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides,

(a2) be unsaturated compound with epoxy radicals or oxetanyl,

(a3) be above-mentioned (a1) and (a2) in addition olefines unsaturated compound; With

[B] light cationic polymerization initiators.

2. the radiation sensitive resin composition of putting down in writing according to claim 1 that is used to form employed projection of vertical alignment-type liquid crystal display device and/or separator is characterized in that: further contain [C] thioxanthones compounds.

3. the projection used of a vertical alignment-type liquid crystal display device, this projection is to be formed by claim 1 or 2 radiation sensitive resin compositions of being put down in writing.

4. the separator that uses of a vertical alignment-type liquid crystal display device, this separator is to be formed by claim 1 or 2 radiation sensitive resin compositions of being put down in writing.

5. vertical alignment-type liquid crystal display device, this vertical alignment-type liquid crystal display device comprise the separator that projection that claim 3 is put down in writing and/or claim 4 are put down in writing.

6. method that forms projection and/or separator is characterized in that: comprise following operation at least,

(1) operation of filming of the radiation-ray sensitive composition that formation claim 1 is put down in writing on substrate;

(2) to the operation of this at least a portion of filming irradiation radioactive ray;

(3) developing procedure;

(4) heating process.

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